在热力学控制下进行 - 硫氧化物 - 交换,用于在热力学控制下进行非对称的基聚合物合成
Jonathan Clayden1, David Mitjans, Latifa H Youssef
1Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK. j.p.clayden@man.ac.uk
Journal of the American Chemical Society
|May 9, 2002
概括
这项研究引入了一种新的动态分辨率方法,用于制造基纯芳胺. 该工艺使用硫氧化物组来控制构型,使有价值的体化合物的高效合成成为可能.
科学领域:
- 有机化学 有机化学
- 立体化学是一种立体化学.
- 合成方法论 合成方法论
背景情况:
- 芳胺具有立体的Ar-CO轴.
- 控制芳胺中的亚特罗皮体是具有挑战性的.
- 现有的方法缺乏效率和反选择性.
研究的目的:
- 开发一种用于芳胺的动态分辨的新方法.
- 为了合成高度染丰富的亚特罗皮索米三级芳胺.
- 使用硫氧化物替代剂引入强大的形状偏差.
主要方法:
- 芳香胺基的整形化.
- 与 (-) - 甲基p-toluenesulfinate 的反应,引入硫氧化物.
- 使用t-BuLi进行硫氧化物-交换.
- 电友性捕获再生的有机.
主要成果:
- 硫氧化物替代剂会诱导强烈的形状偏差.
- 快速平衡导致一个单独的人口 diastereoisomeric Ar-CO atropisomer.
- 在这种过程中,能再生出纯净的和形状稳定的正极质化胺基.
- 电友性捕获产生了高度化丰富的化胺.
结论:
- 描述的方法在热力学控制下实现动态分辨率.
- 这一策略提供了有效的接触到化纯的化三级芳胺.
- 暂时将替换为硫氧化物,然后重新替换为,是这一过程的关键.
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